DE961079C - Process for the catalytic hydrogenation of the mixture from the cleavage of cumene hydroperoxide - Google Patents
Process for the catalytic hydrogenation of the mixture from the cleavage of cumene hydroperoxideInfo
- Publication number
- DE961079C DE961079C DER13356A DER0013356A DE961079C DE 961079 C DE961079 C DE 961079C DE R13356 A DER13356 A DE R13356A DE R0013356 A DER0013356 A DE R0013356A DE 961079 C DE961079 C DE 961079C
- Authority
- DE
- Germany
- Prior art keywords
- mixture
- cumene
- cleavage
- cumene hydroperoxide
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims description 8
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 title claims description 3
- 238000003776 cleavage reaction Methods 0.000 title claims description 3
- 230000007017 scission Effects 0.000 title claims description 3
- 238000000034 method Methods 0.000 title claims 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001908 cumenes Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Es ist bekannt, daß man bei der Aufarbeitung des Phenol und Aceton enthaltenden Gemisches aus der Cumolhydroperoxyd-Spaltung einen Teil des in die Reaktion eingesetzten Cumols wiedergewinnt, das nicht umgesetzt ist. Dieses Cumol enthält gewisse Mengen a-Methylstyrol; letzteres muß aus der Mischung abgetrennt werden, wenn man das Cumol wieder zur Oxydation verwenden will (vgl. It is known that when working up the phenol and acetone containing mixture from the cumene hydroperoxide cleavage part of the in the Reaction recovered cumene used, which is not converted. This cumene contains certain amounts of α-methylstyrene; the latter must be separated from the mixture if you want to use the cumene for oxidation again (cf.
Fortuin und Waterman, Chemical Engineering Science [I953]" 5. 185). Die Destillation der Cumol - a - Methylstyrol - Gemische erfordert erheblichen Aufwand an Apparatur und laufend hohe Betriebskosten. Es ist deshalb vorgeschlagen worden, diese als unerwünscht für die Oxydation erkannte Verbindung durch katalytische Hydrierung in flüssiger Phase bei go bis I00° in Cumol zurückzuverwandeln (USA.-Patentschriften 2 628 983, 2 628 984), doch wurde hierbei als Katalysator Raney-Nickel verwendet (vgl. die deutsche Patentschrift 870 107 und französische Patentschrift 961 022, Beispiel Io). Zwar gelingt es hierbei, das a-Methylstyrol praktisch vollständig aufzuhydrieren, aber es findet gleichzeitig in geringem Umfange eine Hydrierung des Benzolringes statt. Die Anwesenheit von im Ring hydrierten Verbindungen, wie beispielsweise Isopropylcyclohexan und Cyclohexanol, ist aber bei der Oxydation des Cumols sehr unerwünscht.Fortuin and Waterman, Chemical Engineering Science [1953] "p. 185). The distillation of the cumene-α-methylstyrene mixtures requires considerable effort in terms of equipment and continuously high operating costs. It has therefore been suggested this compound recognized as undesirable for the oxidation by catalytic hydrogenation convert back to cumene in the liquid phase at 0 to 100 ° (USA patents 2,628,983, 2,628,984), but Raney nickel was used as the catalyst (see German patent specification 870 107 and French patent specification 961 022, Example Io). It is possible here to practically completely remove the a-methylstyrene hydrogenation, but at the same time there is a small amount of hydrogenation of the benzene ring instead. The presence of compounds hydrogenated in the ring, such as for example isopropylcyclohexane and cyclohexanol, but is in the oxidation of cumene is very undesirable.
Es wurde nun gefunden, daß man das eingangs erwähnte Gemisch bei Temperaturen wesentlich unter I00° glatt hydrieren kann, wenn man die Hydrierung bei gewöhnlichem oder erhöhtem Druck, z. B. 80 at und mehr, und in Gegenwart eines mild wirkenden Katalysators durchführt, der eine selektive Hydrierung ermöglicht und nicht die Anlagerung von Wasserstoff an den Benzolkern begünstigt. Solche Katalysatoren sind auf der Grundlage von Nickel auf Trägerstoffgrundlage aufgebaut. It has now been found that the mixture mentioned at the beginning can be used Temperatures well below 100 ° can hydrogenate smoothly if you use the hydrogenation at ordinary or elevated pressure, e.g. B. 80 at and more, and in the presence of one Carries out a mild catalyst that enables selective hydrogenation and does not favor the addition of hydrogen to the benzene nucleus. Such catalysts are based on nickel on a carrier basis.
Beispiel I In 200 Teilen Wasser löst man 29 Teile Nickelnitrat und fügt 100 Teile eines grobkörnigen Kieselsäuregels hinzu. Die Mischung wird in der Wärme mit I4,6 Teilen Natriumcarbonat gefällt, abgesaugt, sechsmal mit der doppelten Menge warmen Wassers gewaschen; das Produkt wird I2 Stunden bei 100 0.getrocknet, sodann 4 Stunden bei 3500 im Wasserstoffstrom reduziert. Example I 29 parts of nickel nitrate are dissolved in 200 parts of water adds 100 parts of a coarse-grained silica gel. The mixture is in the Heat precipitated with 14.6 parts of sodium carbonate, filtered off with suction, six times with twice as much Amount of warm water washed; the product is dried for 12 hours at 100 °, then reduced for 4 hours at 3500 in a stream of hydrogen.
Man preßt nun auf I Teil Katalysator 8 Teile eines etwa I0 °/e a-Methylstyrol enthaltenden Cumols bei 530 unter 85 bis go at durch den Hydrierofen, wobei man dafür sorgt, daß die Temperatur zwischen 50 und 600 gehalten wird. Das erhaltene Produkt hat einen a-Methylstyrolgehalt von o bis höchstens o,IO/o und einen Brechungsindex n29 = I,49I2. 8 parts of an approximately 10 ° / e α-methylstyrene are now pressed onto 1 part of the catalyst containing cumene at 530 under 85 to go at through the hydrogenation furnace, whereby one ensures that the temperature is kept between 50 and 600. The received The product has an α-methylstyrene content of o to a maximum of o, IO / o and a refractive index n29 = I, 49I2.
Eine für die Durchführung der Hydrierung geeignete Anlage ist beispielsweise in der beigefügten Schemazeichnung wiedergegeben. Aus einem Vorratstank I wird das a-Methylstyrol-Cumol-Gemisch über die Leitung 2 und die Einspritzpumpe 3 in den z. B. 8ovo 1 fassenden Hochdruckofen 4 eingeführt, der mit dem Nickel-Kieselsäuregel-Katalysator beschickt ist und mittels der Kühlschlange 5 durch Wasser gekühlt werden kann. Im Gegenstrom zu dem flüssigen Produkt wird Wasserstoff unter IOO at eingepreßt, der aus der Leitung 6 über den Zwischenbehälter 7 und den Hochdruckverdichter 8 dem Ofen 4 zugeführt wird. Das aufhydrierte Produkt verläßt den Ofen 4 über die Leitung g zu dem Entspannungsgefäß IO; dort wird auf etwa 20 at entspannt und der dabei frei werdende Wasserstoff über die Leitung II in den Zwischenbehälter 7 zurückgeführt. Das im Abscheider IO entlastete Produkt wird über den Kühler 12 in den Behälter I3 überführt und dort völlig entspannt. Da in dem Produkt bei 20 at noch eine Restmenge Wasserstoff gelöst bleibt, ist es zweckmäßig, den im Behälter I3 frei werdenden Wasserstoff wieder auf den Druck aufzupressen, mit dein der Frischwasserstoff über die Leitung 6 der Anlage geliefert wird. In dem Hochdruckofen 4 sind in der üblichen Weise Meßstellen 14 eingebaut, mit denen die Temperatur überwacht wird. A plant suitable for carrying out the hydrogenation is, for example reproduced in the attached schematic drawing. This becomes from a storage tank I. a-methylstyrene-cumene mixture via line 2 and the injection pump 3 into the z. B. 8ovo 1 high pressure furnace 4 introduced with the nickel-silica gel catalyst is charged and can be cooled by water by means of the cooling coil 5. in the Countercurrent to the liquid product, hydrogen is injected under 100 atm, the from the line 6 via the intermediate container 7 and the high pressure compressor 8 dem Furnace 4 is fed. The hydrogenated product leaves the furnace 4 via the line g to the expansion vessel IO; there it is relaxed to about 20 at and that at the same time Released hydrogen is returned to the intermediate container 7 via line II. The product relieved of pressure in the separator IO is fed into the container via the cooler 12 I3 transferred and completely relaxed there. There is still a residual amount in the product at 20 at Hydrogen remains dissolved, it is advisable to use the released in container I3 To pressurize hydrogen again on the pressure, with which the fresh hydrogen over the line 6 of the system is supplied. In the high pressure furnace 4 are in the usual Way measuring points 14 built in, with which the temperature is monitored.
Das erhaltene Cumol kann ohne weitere Nachbehandlung aus dem System über die Förderpumpe I5 wieder der Oxydationsanlage oder sonstigen Verwendungszwecken zugeführt werden. The cumene obtained can be removed from the system without further aftertreatment via the feed pump I5 back to the oxidation system or other uses are fed.
Die selektive Hydrierung des a-Methylstyrols gelingt auch dann, wenn man ohne Druck arbeitet. The selective hydrogenation of the a-methylstyrene succeeds even if you work without pressure.
Beispiel 2 Man leitet durch ein Kontaktrohr, das mit einem nach Beispiel I hergestellten Nickelkatalysator beschickt ist, ein etwa 120/0 a-Methylstyrol enthaltendes Cumol, wobei man die Temperatur im Innern des Kontaktrohres durch eine geeignete Mantelbeheizung auf 50 bis 550 hält und gleichzeitig dem Kontaktraum Wasserstoff zuführt. Man erhält bei geeignet gewähltem Durchsatz ein wasserhelles Hydrierungsprodukt; es enthält 0,05 0/o a-Methylstyrol und erweist sich durch den Brechungsindex (nD°= I,49I2) als praktisch reines Cumol. Example 2 It is passed through a contact tube which is connected to one according to Example I prepared nickel catalyst is charged, a about 120/0 a-methylstyrene containing Cumene, whereby the temperature inside the contact tube by a suitable Jacket heating to 50 to 550 holds and at the same time the contact space hydrogen feeds. With a suitably selected throughput, a water-white hydrogenation product is obtained; it contains 0.05% α-methylstyrene and is shown by the refractive index (nD ° = I, 49I2) as practically pure cumene.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER13356A DE961079C (en) | 1954-01-17 | 1954-01-17 | Process for the catalytic hydrogenation of the mixture from the cleavage of cumene hydroperoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER13356A DE961079C (en) | 1954-01-17 | 1954-01-17 | Process for the catalytic hydrogenation of the mixture from the cleavage of cumene hydroperoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE961079C true DE961079C (en) | 1957-04-04 |
Family
ID=7399011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DER13356A Expired DE961079C (en) | 1954-01-17 | 1954-01-17 | Process for the catalytic hydrogenation of the mixture from the cleavage of cumene hydroperoxide |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE961079C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1134361B (en) * | 1960-04-11 | 1962-08-09 | Phenolchemie Ges Mit Beschraen | Process for the hydrogenation of mixtures containing methylstyrene from cumene hydroperoxide cleavage |
| DE1219035B (en) * | 1961-04-26 | 1966-06-16 | Inst Gorjutschich Iskopajemych | Process for working up the distillation residues which have been obtained in the production of phenol by splitting cumene hydroperoxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE860948C (en) * | 1949-08-19 | 1952-12-29 | Distillers Co Yeast Ltd | Process for the preparation of hydrogenation catalysts |
| DE870107C (en) * | 1949-12-07 | 1953-03-09 | Distillers Co Yeast Ltd | Process for the catalytic hydrogenation of organic compounds |
-
1954
- 1954-01-17 DE DER13356A patent/DE961079C/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE860948C (en) * | 1949-08-19 | 1952-12-29 | Distillers Co Yeast Ltd | Process for the preparation of hydrogenation catalysts |
| DE870107C (en) * | 1949-12-07 | 1953-03-09 | Distillers Co Yeast Ltd | Process for the catalytic hydrogenation of organic compounds |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1134361B (en) * | 1960-04-11 | 1962-08-09 | Phenolchemie Ges Mit Beschraen | Process for the hydrogenation of mixtures containing methylstyrene from cumene hydroperoxide cleavage |
| DE1219035B (en) * | 1961-04-26 | 1966-06-16 | Inst Gorjutschich Iskopajemych | Process for working up the distillation residues which have been obtained in the production of phenol by splitting cumene hydroperoxide |
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